Optical glass

ABSTRACT

An optical glass of a B 2  O 3  --SiO 2  --La 2  O 3  --Yb 2  O 3  system and additionally containing SnO 2  is stable in spectral transmissivity, is scarcely liable to tinting and has high refractive and low dispersive characteristics.

BACKGROUND OF THE INVENTION

This invention relates to an optical glass and, more particularly, to an optical glass of a B₂ O₃ --SiO₂ --SnO₂ --La₂ O₃ --Yb₂ O₃ system which is stable in spectral transmissivity and is scarcely liable to tinting and has optical constants in a high refractive and low dispersive region on the left side of a line a connecting a point where nd is 1.68 and νd is 56.0 and a point where nd is 1.82 and νd is 45.0 in the co-ordinates shown in FIG. 1 of the accompanying drawings.

There is disclosed in Japanese laid-open patent publication 2717/1976 an optical glass which has substantially the same optical constants as the present invention and consists essentially of a B₂ O₃ --La₂ O₃ --Yb₂ O₃ system. This prior art optical glass is not stable in spectral transmissivity due to its melting conditions and besides is liable to tinting. The prior art optical glass therefore is disadvantageous when it is used as high grade lenses suitable for taking colour pictures.

SUMMARY OF THE INVENTION

It is, therefore, an object of the present invention to provide an optical glass which has eliminated the above described disadvantage of the prior art optical glass.

Laborious studies and experiments made by the inventors of the present invention have resulted in a finding that instability in spectral transmissivity due to variation in melting conditions can be prevented and a tendency to tinting can be decreased by introducing SnO₂ as an essential ingredient into an optical glass of a B₂ O₃ --SiO₂ --La₂ O₃ --Yb₂ O₃ system.

According to the present invention, there is provided an optical glass having refractive index (nd) within a range of 1.68 to 1.82 and Abbe number (νd) greater than values on a line connecting a point where nd is 1.68 and νd is 56.0 and a point where nd is 1.82 and νd is 45.0 in an nd-νd rectangular coordinates representative of optical constants and substantially consisting of a composition in weight percent of 17.0-45.0% B₂ O₃, 0.5-10.0% SiO₂, the total of said B₂ O₃ and SiO₂ being 24.0 to 47.0%, 0.05 to 4.0% SnO₂ 20.0 to 50.0% La₂ O₃ 1.0 to 35.0% Yb₂ O₃, 0 to 35.0% Gd₂ O₃, 0 to 15.0% Y₂ O₃, the total of said La₂ O₃, Yb₂ O₃, Gd₂ O₃ and Y₂ O₃ being 43.0 to 68.0%, 0 to 3.0% Al₂ O₃, 0 to 5.0% GeO₂, 0 to 10.0% ZrO₂, 0 to 8.0% Ta₂ O₅, 0 to 3.0% Nb₂ O₅, 0 to 5.0% MgO, 0 to 10.0% CaO, 0 to 10.0% SrO, 0 to 10.0% BaO, 0 to 8.0% ZnO, the total of said MgO, CaO, SrO, BaO and ZnO being 0 to 10.0%, one or more ingredients selected from the group consisting of Li₂ O, Na₂ O and K₂ O, the total of said Li₂ O, Na₂ O and K₂ O being 0 to 0.5%, a fluoride or fluorides in substitution, in part or in whole, for the oxide or oxides of the same element or elements as said fluoride or fluorides among the ingredients of said composition, the total amount of F contained in said fluoride or fluorides being 0 to 8.0%, and 0 to 0.2% As₂ O₃ and/or Sb₂ O₃.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings,

FIG. 1 is a graphical diagram showing the optical constant region of the optical glass according to the present invention; and

FIGS. 2 through 4 are graphical diagram showing variations in spectral transmissivity caused by differences in melting conditions of the optical glass of the present invention in comparison with those of prior art optical glasses.

DETAILED DESCRIPTION OF THE INVENTION

In the optical glass made according to the present invention, the above described content ranges of the respective ingredients have been selected for reasons stated below.

If the content of B₂ O₃ is less than 17%, a devitrification tendency increases whereas if it exceeds 45%, desired optical constants cannot be obtained.

SiO₂ contributes to increasing viscosity of the glass and decreasing devitrification and it is particularly an indispensable ingredient in melting of the glass in a large production scale. If the content of SiO₂ is less then 0.5%, the effect of decreasing devitrification is remarkably reduced whereas if the content exceeds 10%, the SiO₂ material becomes hard to melt so that a homogeneous glass cannot be obtained.

If the total amount of B₂ O₃ and SiO₂ is less than 24%, the devitrification tendency increases whereas if it exceeds 47%, the desired optical constants cannot be maintained.

In the optical glass according to the present invention, SnO₂ is effective for preventing instability in spectral transmissivity caused by variation in melting conditions and decreasing the tendency to tinting. Besides, SnO₂ contributes to preventing devitrification. If, however, the content of SnO₂ is less than 0.05%, these effects cannot be obtained to a satisfactory degree, whereas if the content of SnO₂ exceeds 4.0%, the glass is extremely tinted contrary to expectation.

La₂ O₃ is an important ingredient for providing high refractive and low dispersive characteristics to the glass. If the content thereof is less than 20%, the desired optical constants cannot be obtained whereas if it exceeds 50%, devitrification remarkably increases.

Yb₂ O₃ is an essential ingredient for the optical glass of the present invention having high refractive and low dispersive characteristics, for Yb₂ O₃ provides the glass with optical properties which are closely similar to those of La₂ O₃ without adversely affecting resistivity to devitrification. If the content of Yb₂ O₃ is less than 1.0%, such effect cannot be obtained to a satisfactory extent. The content exceeding 35.0% is undesirable because devitrification increases.

The following ingredients may be included in the optical glass according to the present invention within the prescribed content ranges for preventing devitrification, improving melting property, correcting optical constants and like purposes.

Gd₂ O₃ and Y₂ O₃ respectively provide the glass with optical properties resembling those of La₂ O₃ and besides make the glass stable. If, however, the contents of Gd₂ O₃ and Y₂ O₃ exceed 35.0% and 15.0% respectively, devitrification remarkably increases. Further, if the total amount of these ingredients and La₂ O₃ and Yb₂ O₃ is less than 43.0%, the desired optical constants cannot be obtained whereas if the total amount exceeds 68.0%, devitrification remarkably increases.

Al₂ O₃ is effective for increasing viscosity of the glass and decreasing devitrification, but if the content thereof exceeds 3.0%, devitrification increases.

GeO₂ is useful ingredient for making the glass stable. If the content thereof exceeds 5.0%, it occasions increase in dispersion and the desired optical constants cannot be obtained.

ZrO₂ is an effective ingredient for increasing refractivity and making the glass stable. If the content thereof exceeds 10.0%, melting of ZrO₂ into the glass becomes difficult.

Ta₂ O₅ and Nb₂ O₅ are effective ingredients for increasing refractivity and making the glass stable. If the contents thereof exceed 8.0% and 3.0% respectively, dispersion increases and the desired optical constants cannot be obtained.

MgO, CaO, SrO, BaO and ZnO are effective for readily homogenizing the glass. If the respective contents of these ingredients exceed 5.0%, 10.0%, 10.0%, 10.0% and 8.0%, the tendency to devitrification sharply increases. Further, the total amount of these ingredients should not exceed 10.0%, for if it exceeds 10.0%, the tendency to devitrification increases.

Li₂ O, Na₂ O and K₂ O facilitate melting of the SiO₂ material into the glass and homogenizing the glass. If, however, the total amount of one or more of these ingredients exceeds 0.5%, the devitrification tendency sharply increases.

F is a useful ingredient for lowering a liquidus temperature and decreasing devitrification if it is included in the glass by substituting, in part or in whole, one or more of the above described metal oxides by corresponding fluoride or fluorides, e.g. NaF, CaF₂, BaF₂, AlF₃, LaF₃ etc. If the content thereof exceeds 8.0%, a homogenous glass cannot be obtained.

As₂ O₃ and/or Sb₂ O₃ is employed for defoaming of the glass. If the contents thereof exceeds 0.2%, the devitrification tendency sharply increases.

Examples of compositions of the optical glass according to the present invention are shown in Table 1 under No. 1 through No. 20. Refractive indices and Abbe values of these examples are shown in Table 2. In Tables 1 and 2, glasses designated by reference characters S1 through S5 are prior art glasses listed for comparison. The glass S1 resembles the composition of the glass No. 3, the glass S2 resembles the glass No. 5 and the glass S3 resembles the glass No. 12. These prior art glasses S1, S2 and S3 all have optical constants which come within the high refractive and low dispersive optical property region of the optical glass according to the present invention but they are different from the glass of the present invention in that they do not contain SnO₂. The glass S4 is of a higher refractivity and lower despersion than the glass of the present invention. The glass S5 is of a refractivity range which is similar to that of the glass of the present invention but its Abbe value falls short of the condition for the glass of the present invention.

Table 2 shows, with respect to the examples No. 1 through No. 20 and the prior art glasses S1 through S5, light wavelength at which transmissivity is 80% in two glass specimens (A) and (B) obtained under different melting conditions and difference Δλ between the specimens (A) and (B) in the wavelengths at which transmissivity is 80%. The specimen (A) is obtained by melting the material at 1350° C. for two hours, and thereafter cooling the melt promptly and casting it in a mould. The specimen (B) is obtained by melting the material at 1350° C. for two hours, maintaining the melt at 1200° C. for three hours, and thereafter cooling the melt promptly and casting it in a mould.

As will be apparent from Table 2, difference Δλ in the 80% transmissivity wavelength between the specimens (A) and (B) is 0 to 3 in the optical glass according to the invention, whereas Δλ is a relatively large value of 13 to 15 in the glasses S1-S3 which are of compositions similar to the present invention except that they do not contain SnO₂. The effect of the present invention will be apparent from the comparison of the values of Δλ. It would be noted that a glass such as S4 which is of extremely high refractive and low dispersive characteristics, i.e., a glass having optical constants outside of the range of optical constants of the present invention, can have a smaller value of Δλ if it contains SnO₂ but the devitrification tendency increases by inclusion of SnO₂ to such a degree that melting of the glass in a large scale becomes difficult. Accordingly, addition of SnO₂ in such extremely high refractive, low dispersive glass is not proper. A glass such as S5 having optical constants outside of the range of optical constants of the present invention contains a great deal of Ta₂ O₅, is stable in its spectral transmissivity, and is not liable to tinting, so that there is no need for adding SnO₂. Further, generally speaking, glasses of optical constants which are on the right side of the line a in FIG. 1 can be readily produced without adding expensive Yb₂ O₃ as in the glass according to the invention.

FIG. 2 shows results of comparing spectral transmissivity of the specimen (A) with that of the specimen (B) with respect to the glass No. 3 and the prior art glass S1 which is of a composition similar to that of the glass No. 3 but including no SnO₂. FIG. 3 shows results of like comparison with respect to the glass No. 5 and the glass S2, and FIG. 4 those with respect to the glass No. 12 and the glass S3.

It will be understood from FIGS. 2 through 4 that there are noticeable differences in the spectral transmissivity curves of the prior art glasses S1 through S3 depending upon melting conditions so that these prior art glasses are not stable, whereas there is no substantial difference in the spectral transmissivity curves of the glasses of the present invention despite the differences in the melting conditions so that the optical glass of the present invention is very stable. Besides, the transmissivity of the optical glass of the present invention is by far superior to that of the prior art glasses.

As described in the foregoing, the optical glasses according to the present invention has an extremely high refractive and low dispersive optical property range on the left side of the line a connecting the point where nd is 1.68 and νd is 56.0 and the point where nd is 1.82 and νd is 45.0 in the nd-νd rectangular coordinates. In comparison with the prior art optical glasses, the optical glass according to the present invention has a high resistivity to tinting and its spectral transmissivity does not substantially change despite variation in the melting conditions. Accordingly, it is most suited for a material of a high grade lense for taking a color picture.

The optical glass according to the invention can be readily manufactured by melting a batch of oxides, carbonates, nitrates, fluorides etc. at 1300° C.-1400° C. in a platinum crucible or the like, defoaming and stirring the molten glass to homogenize it, lowering the temperature, casting the molten glass into a mould and thereafter annealing it.

                                      TABLE 1                                      __________________________________________________________________________     Composition           (weight %)                                               Example                                                                             B.sub.2 O.sub.3                                                                   SiO.sub.2                                                                         SnO.sub.2                                                                         La.sub.2 O.sub.3                                                                   Yb.sub.2 O.sub.3                                                                   Others                                                   __________________________________________________________________________     No. 1                                                                               30.0                                                                              4.0                                                                               1.0                                                                               42.0                                                                               23.0                                                         No. 2                                                                               32.0                                                                              1.0                                                                               1.5                                                                               40.0                                                                               25.5                                                         No. 3                                                                               36.0                                                                              1.5                                                                               1.5                                                                               38.0                                                                               18.0                                                                               Gd.sub.2 O.sub.3                                                                5.0                                                     No. 4                                                                               21.2                                                                              10.0                                                                              0.5                                                                               35.0                                                                               10.0                                                                               Gd.sub.2 O.sub.3                                                                   Li.sub.2 O                                                                 23.0                                                                               0.3                                                  No. 5                                                                               28.4                                                                              1.0                                                                               0.6                                                                               34.0                                                                               16.0                                                                               Gd.sub.2 O.sub.3                                                                   ZrO.sub.2                                                                  10.0                                                                               10.0                                                 No. 6                                                                               28.5                                                                              0.5                                                                               0.3                                                                               40.0                                                                               7.0 Gd.sub.2 O.sub.3                                                                   ZrO.sub.2                                                                          GeO.sub.2                                                              14.0                                                                               4.7 5.0                                              No. 7                                                                               32.0                                                                              1.5                                                                               0.5                                                                               20.0                                                                               1.0 Gd.sub.2 O.sub.3                                                                   BaO                                                                        35.0                                                                               10.0                                                 No. 8                                                                               17.0                                                                              7.0                                                                               0.8                                                                               30.0                                                                               2.4 Gd.sub.2 O.sub.3                                                                   ZrO.sub.3                                                                          Ta.sub.2 O.sub.5                                                       30.0                                                                               4.8 8.0                                              No. 9                                                                               36.5                                                                              1.7                                                                               3.0                                                                               33.0                                                                               5.0 Gd.sub.2 O.sub.3                                                                   BaO Li.sub.2 O                                                             19.0                                                                               1.5 0.3                                              No. 10                                                                              35.8                                                                              3.2                                                                               0.8                                                                               36.0                                                                               1.0 Y.sub.2 O.sub.3                                                                    ZrO.sub.2                                                                          CaO                                                                    15.0                                                                               5.7 2.5                                              No. 11                                                                              32.0                                                                              5.5                                                                               2.0                                                                               50.0                                                                               10.0                                                                               Li.sub.2 O                                                                      0.5                                                     No. 12                                                                              45.0                                                                              2.0                                                                               0.5                                                                               33.0                                                                               10.0                                                                               CaO                                                                             9.5                                                     No. 13                                                                              42.0                                                                              0.9                                                                               0.3                                                                               40.0                                                                               5.6 Al.sub.2 O.sub.3                                                                   MgO SrO Sb.sub.2 O.sub.3                                                    3.0                                                                               5.0 3.0 0.2                                          No. 14                                                                              41.0                                                                              4.6                                                                               0.05                                                                              38.0                                                                               5.65                                                                               BaO ZnO Na.sub.2 O                                                                         K.sub.2 O                                                                          AS.sub.2 O.sub.3                                                2.0                                                                               8.0 0.3 0.2 0.2                                      No. 15                                                                              39.0                                                                              5.1                                                                               1.0                                                                               39.0                                                                               5.9 SrO                                                                            10.0                                                     No. 16                                                                              40.7                                                                              3.1                                                                               4.0                                                                               40.0                                                                               5.7 CaO K.sub.2 O                                                                   6.0                                                                               0.5                                                  No. 17                                                                              29.0                                                                              2.4                                                                               0.6                                                                               25.0                                                                               35.0                                                                               ZrO.sub.2                                                                          ZnO                                                                         7.0                                                                               1.0                                                  No. 18                                                                              33.5                                                                              1.0                                                                               0.1                                                                               47.4                                                                               15.0                                                                               Nb.sub.2 O.sub.5                                                                3.0                                                     No. 19                                                                              37.3                                                                              2.1                                                                               0.5                                                                               20.0                                                                               8.4 CaO     LaE.sub.3                                                               4.2    27.5                                             No. 20                                                                              41.0                                                                              1.0                                                                               0.1                                                                               35.1                                                                               12.2                                                                               Li.sub.2 O                                                                         SrF.sub.2                                                                          LaF.sub.3                                                               0.5                                                                               3.6 6.5                                              S 1  36.0                                                                              1.0   41.0                                                                               18.0                                                                               Gd.sub.2 O.sub.3                                                                4.0                                                     S 2  28.5                                                                              1.0   34.2                                                                               16.1                                                                               Gd.sub.2 O.sub.3                                                                   ZrO.sub.2                                                                  10.1                                                                               10.1                                                 S 3  44.0                                                                              1.0   35.0                                                                               10.0                                                                               CaO                                                                            10.0                                                     S 4  21.9     33.3                                                                               14.3                                                                               Ta.sub.2 O.sub.5                                                                   WO.sub.3                                                                   25.7                                                                               4.8                                                  S 5  28.6     38.1                                                                               16.2                                                                               Ta.sub.2 O.sub.5                                                                   Al.sub.2 O.sub.3                                                           12.3                                                                               4.8                                                  __________________________________________________________________________

                  TABLE 2                                                          ______________________________________                                                           80%                                                                 Optical    transmissivity                                                      constants  wavelength (nm                                                                               Δλ                                Example  nd       νd   (A)    (B)    (nm)                                   ______________________________________                                         No. 1    1.7418   53.5    382    380    2                                      No. 2    1.7460   53.4    395    396    1                                      No. 3    1.7250   54.8    369    368    1                                      No. 4    1.7585   52.4    370    370    0                                      No. 5    1.7845   49.5    385    388    3                                      No. 6    1.7740   50.3    374    374    0                                      No. 7    1.7290   54.6    385    383    2                                      No. 8    1.8200   46.3    400    400    0                                      No. 9    1.7250   54.3    392    393    1                                      No. 10   1.7375   52.6    375    375    0                                      No. 11   1.7343   54.0    388    388    0                                      No. 12   1.6805   57.7    375    377    2                                      No. 13   1.6858   56.1    384    383    1                                      No. 14   1.6948   55.6    389    386    3                                      No. 15   1.6920   56.1    368    368    0                                      No. 16   1.7030   55.8    390    392    2                                      No. 17   1.7610   50.9    382    382    0                                      No. 18   1.7586   50.8    392    394    2                                      No. 19   1.6858   58.2    372    372    0                                      No. 20   1.7048   57.2    370    370    0                                      S 1      1.7255   54.7    397    382    15                                     S 2      1.7842   59.5    414    401    13                                     S 3      1.6893   56.6    410    397    13                                     S 4      1.8379   40.0    425    416    9                                      S 5      1.7660   46.7    380    382    2                                      ______________________________________                                     

What is claimed is:
 1. An optical glass having refractive index (nd) within a range of 1.68 to 1.82 and Abbe number (νd) greater than values on a line connecting a point where nd is 1.68 and νd is 56.0 and a point where nd is 1.82 and νd is 45.0 in an nd-νd rectangular coordinates representative of optical constants and substantially consisting of a composition in weight percent of 17.0 to 45.0% B₂ O₃, 0.5 to 10.0% SiO₂, the total of said B₂ O₃ and SiO₂ being 24.0 to 47.0%, 0.05 to 4.0% SnO₂, 20.0 to 50.0% La₂ O₃ 1.0 to 35.0% Yb₂ O₃, 0 to 35.0% Gd₂ O₃, 0 to 15.0% Y₂ O₃ the total of said La₂ O₃, Yb₂ O₃, Gd₂ O₃ and Y.sub. 2 O₃ being 43.0 to 68.0%, 0 to 3.0% Al₂ O₃, 0 to 5.0% GeO₂, 0 to 10.0% ZrO₂, 0 to 8.0 Ta₂ O₅, 0 to 3.0% Nb₂ O₅, 0 to 5.0% MgO, 0 to 10.0% CaO, 0 to 10.0% SrO, 0 to 10.0% BaO, 0 to 8.0% ZnO, the total of said MgO, CaO, SrO, BaO and ZnO being 0 to 10.0%, one or more ingredients selected from the group consisting of Li₂ O, Na₂ O and K₂ O, the total of said Li₂ O, Na₂ O and K₂ O being 0 to 0.5%, a fluoride or fluorides in substitution, in part or in whole, for the oxide or oxides of the same element or elements as said fluoride or fluorides among the ingredients of said composition, the total amount of F contained in said fluoride or fluorides being 0 to 8.0%, and 0 to 0.2% As₂ O₃ and/or Sb₂ O₃. 